A Method for the Measurement of the Water Solubility Distribution of Atmospheric Organic Aerosols.

A method for the measurement of the water solubility distribution of atmospheric organic aerosols is presented. This method is based on the extraction of organic aerosols collected on filters, using different amounts of water and measurement of the corresponding water-soluble organic carbon concentration. The solubility distribution is then estimated using the solubility basis set. The method was applied on both ambient and source-specific aerosols. Approximately 60% of the atmospheric urban organic aerosol analyzed had water solubility higher than 0.6 g L-1. Around 10% of the fresh cooking organic aerosol had water solubility higher than 10 g L-1, while 80% of the total fresh cooking organic aerosol had solubility lower than 0.1 g L-1. The ambient measurements suggested that the solubility distributions are roughly consistent with the positive matrix factorization analysis results determined during the analysis of the high-resolution time-of-flight aerosol mass spectrometry data. Most of the oxidized organic aerosol appears to have water solubility above 0.6 g L-1, while the hydrocarbon-like organic aerosol and cooking organic aerosol have water solubility less than 0.002 and 0.1 g L-1, respectively. The biomass burning organic aerosol seems to have mostly intermediate solubility in water, between 0.04 and 0.6 g L-1. The proposed approach can quantify the solubility distribution in the 0.002-15 g L-1 range. Future extension of the method to higher solubility ranges would be useful for capturing the complete solubility range for atmospheric cloud condensation studies (0.1-100 g L-1).

Physical and Chemical Properties of 3-Methyl-1,2,3-butanetricarboxylic Acid (MBTCA) Aerosol.

The properties and the chemical fate of later generation products of the oxidation of biogenic organic compounds are mostly unknown. The properties of fresh MBTCA aerosol, a later generation product of the oxidation of monoterpenes in the atmosphere, were determined combining an aerosol mass spectrometer (AMS), a thermodenuder, and a scanning mobility particle sizer. Based on its AMS spectrum m/z 141.055 (C7H9O3+) could be used as an MBTCA signature. The MBTCA particle density was 1.43 ± 0.04 g cm-3, its saturation concentration was (1.8 ± 1.3) × 10-3 µg m-3 at 298 K, and its vaporization enthalpy was 150 ± 15 kJ mol-1. After OH radical exposure (∼1.2 days) and UV illumination the average aerosol O:C ratio decreased from 0.72 to 0.58-0.64 suggesting net fragmentation. Our findings suggest that the reactions of MBTCA with OH lead to CO2 loss with or without an oxygen addition.

Urban particulate matter pollution: a tale of five cities.

Five case studies (Athens and Paris in Europe, Pittsburgh and Los Angeles in the United States, and Mexico City in Central America) are used to gain insights into the changing levels, sources, and role of atmospheric chemical processes in air quality in large urban areas as they develop technologically. Fine particulate matter is the focus of our analysis. In all cases reductions of emissions by industrial and transportation sources have resulted in significant improvements in air quality during the last few decades. However, these changes have resulted in the increasing importance of secondary particulate matter (PM) which dominates over primary in most cases. At the same time, long range transport of secondary PM from sources located hundreds of kilometres from the cities is becoming a bigger contributor to the urban PM levels in all seasons. "Non-traditional" sources including cooking, and residential and agricultural biomass burning contribute an increasing fraction of the now reduced fine PM levels. Atmospheric chemistry is found to change the chemical signatures of a number of these sources relatively fast both during the day and night, complicating the corresponding source apportionment.

Detailed Speciation of Non-Methane Volatile Organic Compounds in Exhaust Emissions from Diesel and Gasoline Euro 5 Vehicles Using Online and Offline Measurements.

The characterization of vehicle exhaust emissions of volatile organic compounds (VOCs) is essential to estimate their impact on the formation of secondary organic aerosol (SOA) and, more generally, air quality. This paper revises and updates non-methane volatile organic compounds (NMVOCs) tailpipe emissions of three Euro 5 vehicles during Artemis cold urban (CU) and motorway (MW) cycles. Positive matrix factorization (PMF) analysis is carried out for the first time on proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) datasets of vehicular emission. Statistical analysis helped to associate the emitted VOCs to specific driving conditions, such as the start of the vehicles, the activation of the catalysts, or to specific engine combustion regimes. Merged PTR-ToF-MS and automated thermal desorption gas chromatography mass spectrometer (ATD-GC-MS) datasets provided an exhaustive description of the NMVOC emission factors (EFs) of the vehicles, thus helping to identify and quantify up to 147 individual compounds. In general, emissions during the CU cycle exceed those during the MW cycle. The gasoline direct injection (GDI) vehicle exhibits the highest EF during both CU and MW cycles (252 and 15 mg/km), followed by the port-fuel injection (PFI) vehicle (24 and 0.4 mg/km), and finally the diesel vehicle (15 and 3 mg/km). For all vehicles, emissions are dominated by unburnt fuel and incomplete combustion products. Diesel emissions are mostly represented by oxygenated compounds (65%) and aliphatic hydrocarbons (23%) up to C22, while GDI and PFI exhaust emissions are composed of monoaromatics (68%) and alkanes (15%). Intermediate volatility organic compounds (IVOCs) range from 2.7 to 13% of the emissions, comprising essentially linear alkanes for the diesel vehicle, while naphthalene accounts up to 42% of the IVOC fraction for the gasoline vehicles. This work demonstrates that PMF analysis of PTR-ToF-MS datasets and GC-MS analysis of vehicular emissions provide a revised and deep characterization of vehicular emissions to enrich current emission inventories.

Vehicle and driving characteristics that influence in-cabin particle number concentrations.

In-transit microenvironments experience elevated levels of vehicle-related pollutants such as ultrafine particles. However, in-vehicle particle number concentrations are frequently lower than on-road concentrations due to particle losses inside vehicles. Particle concentration reduction occurs due to a complicated interplay between a vehicle's air-exchange rate (AER), which determines particle influx rate, and particle losses due to surfaces and the in-cabin air filter. Accurate determination of inside-to-outside particle concentration ratios is best made under realistic aerodynamic and AER conditions because these ratios and AER are determined by vehicle speed and ventilation preference, in addition to vehicle characteristics such as age. In this study, 6 vehicles were tested at 76 combinations of driving speeds, ventilation conditions (i.e., outside air or recirculation), and fan settings. Under recirculation conditions, particle number attenuation (number reduction for 10-1000 nm particles) averaged 0.83 ± 0.13 and was strongly negatively correlated with increasing AER, which in turn depended on speed and the age of the vehicle. Under outside air conditions, attenuation averaged 0.33 ± 0.10 and primarily decreased at higher fan settings that increased AER. In general, in-cabin particle number reductions did not vary strongly with particle size, and cabin filters exhibited low removal efficiencies.

Real-Time Assessment of E-Cigarettes and Conventional Cigarettes Emissions: Aerosol Size Distributions, Mass and Number Concentrations.

Cigarette smoke is a complex mixture of chemical compounds which are emitted during the processes of tobacco combustion. Electronic cigarettes (e-cigs) are expected to produce less harmful compounds due to the absence of tobacco leaf combustion. However, potential risks of the passive exposure to the aerosol exhaled by e-cig users have been raised in the last decade. In this study, the aerosols with diameter less than 1 µm (PM1) produced by vaping of various e-cig liquids were compared to those generated by smoking conventional cigarettes in real time. The mass and number concentration along with the number size distribution were measured in a closed room of 35 m3 volume. Our results showed that aerosols emitted from e-cig liquids had a different profile compared to those from conventional cigarettes. Although e-cigs initially produced higher particle mass and number concentrations, their emissions had much shorter lifetime of approximately 10-20 s, in comparison with the conventional and hand-rolling cigarette particulate emissions which had a dissipation time of approximately 1.4 h in a 35 m3 room. E-cigs emitted aerosols which volatilized rapidly, as they probably consisted almost only of propylene glycol and/or vegetable glycerin.

Mass spectra deconvolution of low, medium, and high volatility biogenic secondary organic aerosol.

Secondary organic aerosol (SOA) consists of compounds with a wide range of volatilities and its ambient concentration is sensitive to this volatility distribution. Recent field studies have shown that the typical mass spectrum of ambient oxygenated organic aerosol (OOA) as measured by the Aerodyne Aerosol Mass Spectrometer (AMS) is quite different from the SOA mass spectra reported in smog chamber experiments. Part of this discrepancy is due to the dependence of SOA composition on the organic aerosol concentration. High precursor concentrations lead to higher concentrations of the more volatile species in the produced SOA while at lower concentrations the less volatile compounds dominate the SOA composition. alpha-Pinene, beta-pinene, d-limonene, and beta-caryophyllene ozonolysis experiments were performed at moderate concentration levels. Using a thermodenuder the more volatile SOA species were removed achieving even lower SOA concentration. The less volatile fraction was then chemically characterized by an AMS. The signal fraction of m/z44, and thus the concentration of C02+, is significantly higher for the less volatile SOA. High NO(x) conditions result in less oxidized SOA than low NO(x) conditions, while increasing relative humidity levels results in more oxidized products for limonene but has little effect on alpha-and beta-pinene SOA. Combining a smog chamber with a thermodenuder model employing the volatility basis-set framework, the AMS SOA mass spectrum for each experiment and for each precursor is deconvoluted into low, medium, and high volatility component mass spectra. The spectrum of the surrogate component with the lower volatility is quite similar to that of ambient OOA.